WO2017178575A1 - Catalyseur pourvu d'un revêtement à effet scr - Google Patents

Catalyseur pourvu d'un revêtement à effet scr Download PDF

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Publication number
WO2017178575A1
WO2017178575A1 PCT/EP2017/058900 EP2017058900W WO2017178575A1 WO 2017178575 A1 WO2017178575 A1 WO 2017178575A1 EP 2017058900 W EP2017058900 W EP 2017058900W WO 2017178575 A1 WO2017178575 A1 WO 2017178575A1
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WIPO (PCT)
Prior art keywords
catalyst
scr
catalytically active
zeolite
catalyst substrate
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PCT/EP2017/058900
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German (de)
English (en)
Inventor
Frank Welsch
Stephan Eckhoff
Michael Seyler
Anke Schuler
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Umicore Ag & Co. Kg
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Application filed by Umicore Ag & Co. Kg filed Critical Umicore Ag & Co. Kg
Priority to US16/086,720 priority Critical patent/US20190105650A1/en
Priority to KR1020187032743A priority patent/KR20180127514A/ko
Priority to JP2018543128A priority patent/JP7013378B2/ja
Priority to CN202111514436.9A priority patent/CN114160188A/zh
Priority to EP17716275.7A priority patent/EP3442686A1/fr
Priority to CN201780010184.1A priority patent/CN108712927B/zh
Publication of WO2017178575A1 publication Critical patent/WO2017178575A1/fr
Priority to JP2022005655A priority patent/JP7322206B2/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/763—CHA-type, e.g. Chabazite, LZ-218
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0246—Coatings comprising a zeolite
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2067—Urea
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1021—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20738—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/903—Multi-zoned catalysts
    • B01D2255/9032—Two zones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/92—Dimensions
    • B01D2255/9205—Porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
    • B01D53/9477—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
    • F01N2370/04—Zeolitic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a catalyst with SCR active
  • Exhaust gases from motor vehicles with a predominantly lean-burn internal combustion engine contain, in addition to particulate emissions, in particular the primary emissions carbon monoxide CO, hydrocarbons HC and
  • Nitrogen oxides NOx Due to the relatively high oxygen content of up to 15% by volume, carbon monoxide and hydrocarbons can be rendered relatively harmless by oxidation. The reduction of nitrogen oxides to nitrogen, however, is much more difficult.
  • the presence of oxygen is the selective catalytic reduction (SCR process) by means of ammonia on a suitable catalyst.
  • SCR process selective catalytic reduction
  • the nitrogen oxides to be removed from the exhaust gas are reacted with ammonia to nitrogen and water.
  • ammonia used as reducing agent can be prepared by metering in an ammonia precursor compound, such as, for example, urea,
  • Ammonium carbamate or ammonium formate are made available in the exhaust line and subsequent hydrolysis. Particles can be removed very effectively with the help of particle filters from the exhaust gas. Wall flow filters made of ceramic materials have proven particularly useful. These are from a variety of parallel
  • the channels Built up channels formed by porous walls.
  • the channels are mutually gastight at one of the two ends of the filter
  • first channels are formed, which are open on the first side of the filter and closed on the second side of the filter
  • second channels which are closed on the first side of the filter and open on the second side of the filter.
  • first Inlet exhaust gas can only leave the filter through the second channels, and must flow through the porous walls between the first and second channels for this purpose. As the exhaust passes through the wall, the particles are retained.
  • JPHOl-151706 and WO2005 / 016497 propose coating a wall-flow filter with an SCR catalyst in such a way that the latter penetrates the porous walls (so-called in-wall coating).
  • N 2 0 nitrous oxide
  • WO2015 / 145113 Al discloses a method for reducing N2O emissions in the exhaust gas, which comprises using a small pore zeolite having an SAR of about 3 to about 15, which is about 1 to 5 wt% of an exchanged transition metal having.
  • the present invention relates to a catalyst comprising a catalyst substrate of length L and two different SCR catalytically active materials A and B, wherein the SCR catalytically active material A comprises a Levyne-type zeolite containing ion-exchanged iron and / or copper, and the SCR-catalytically active material B contains a chalcazite-type zeolite containing ion-exchanged iron and / or copper
  • the SCR catalytically active materials A and B are in the form of two material zones A and B, with material zone A extending from the first end of the catalyst substrate over at least part of the length L and material zone B extending from the second end of the catalyst substrate extends over at least part of the length L, or where
  • the catalyst substrate is formed from the SCR catalytically active material A and a matrix component and the SCR catalytically active material B extends in the form of a material zone B over at least part of the length L of the catalyst substrate,
  • the catalyst substrate is formed from the SCR catalytically active material B and a matrix component and the SCR catalytically active material A extends in the form of a material zone A over at least part of the length L of the catalyst substrate.
  • the chalcazite-type zeolite has an SAR (silica to alumina) ratio of 6 to 40, preferably 12 to 40, and more preferably 25 to 40.
  • the Levyne-type zeolite has a SAR value greater than 15, preferably greater than 30, for example from 30 to 50.
  • Candidate zeolites of the chabazite structure type are, for example, the products known under the names chabazite and SSZ-13.
  • Candidate zeolites of the Levyne structure type are, for example, Nu-3, ZK-20 and LZ-132.
  • the term zeolite includes not only aluminosilicates, but also silicoaluminophosphates and
  • Aluminophosphates sometimes referred to as zeolite-like compounds.
  • SAPO-34 and AIPO-34 structure type CHA
  • SAPO-35 and AIPO-35 structure type LEV
  • both the chabazite-type zeolite and the Levyne-type zeolite contain ion-exchanged copper.
  • the amounts of copper are independent of each other in the zeolite of the chabazite structure type and in the zeolite of the Levyne structure type
  • the atomic ratio of copper exchanged in the zeolite to framework aluminum in the zeolite is particularly 0.25 to 0.6 for the zeolite of the chabazite type and the zeolite of the Levyne type.
  • Cu / Al values 0.35-0.5, which corresponds to a theoretical Cu exchange degree of 70-100%.
  • the amounts of iron in the zeolite of the chabazite structure type and in the zeolite of the Levyne structure type are independent of each other
  • the atomic ratio of iron exchanged in the zeolite to framework aluminum in the zeolite is in particular 0.25 to 3 for the zeolite of the chabazite structure type and for the zeolite of the Levyne structure type.
  • the material zone A includes, for example, except the copper or iron exchanged zeolites of Levyne structure type no catalytically active components. However, it may optionally contain auxiliaries, such as binders. Suitable binders are, for example, alumina, titania and zirconia, with alumina being preferred. In
  • Embodiments of the present invention consists of material zone A of Levyne-type zeolites exchanged with copper or iron and of binder.
  • Alumina is preferred as the binder.
  • the material zone B includes, for example, except the exchanged with copper or iron zeolites of chabazite structure type no catalytically active components. However, it may optionally contain auxiliaries, such as binders. Suitable binders are, for example
  • material zone A consists of copper-iron exchanged chabazite-type zeolites, as well as binder. Alumina is preferred as the binder.
  • 20 to 80% by weight of the catalytically active material accounts for material zone B, preferably 40 to 80% by weight, particularly preferably 50 to 70% by weight.
  • the present invention relates to a catalyst comprising a catalyst substrate of length L and two distinct SCR catalytically active materials A and B, wherein the SCR catalytically active material A is a zeolite of the Levyne structure type, the ion-exchanged iron and / or contains copper, and
  • the SCR catalytically active material B comprises a chalcazite-type zeolite containing ion-exchanged iron and / or copper, wherein the SCR catalytically active materials A and B in the form of two
  • Material zones A and B are present, wherein material zone A, starting from the first end of the catalyst substrate at least over a portion of the length L extends and extends from the second end of the catalyst substrate at least over a portion of the length L of material zone B.
  • the exhaust gas preferably flows into the catalyst at the first end of the catalyst substrate and out of the catalyst at the second end of the catalyst substrate.
  • the two material zones A and B can be arranged in various ways on the catalyst substrate, wherein as catalyst substrates, for example so-called flow-through substrates or wall-flow filters can be used.
  • a wall-flow filter is a catalyst substrate comprising channels of length L extending in parallel between first and second ends of the wall-flow filter, which are alternately gas-tight at either the first or second end and which are separated by porous walls.
  • a flow-through substrate is different from one
  • the catalyst substrate may be a wall-flow filter or a flow-through substrate.
  • material zone A extends over the entire length L of the catalyst substrate, while material zone B extends from the second end of the catalyst substrate over 10 to 80% of its length L.
  • material zone B is preferably arranged on material zone A.
  • material zone A extends from the first end of the catalyst substrate over 20 to 90% of its length L, while material zone B extends from the second end over 10 to 70%. its length L extends.
  • material zone A extends from the first end of the catalyst substrate over 20 to 100% of its length L, while material zone B extends over its entire length L.
  • material zone A is preferably arranged on material zone B.
  • the catalyst substrate is designed as a wall-flow filter.
  • the channels, which are open at the first end of the wall-flow filter and closed at the second end, are coated with material zone A, while the channels, which are closed at the first end of the wall-flow filter and open at the second end, are coated with material zone B.
  • Flow-through substrates and wall-flow filters that can be used in accordance with the present invention are known and available on the market. They consist for example of silicon carbide, aluminum titanate or cordierite.
  • the pores of the wall-flow filter are so-called open pores, that is to say they have a connection to the channels. Furthermore, the pores are usually interconnected. This allows, on the one hand, the slight coating of the inner pore surfaces and, on the other hand, an easy passage of the exhaust gas through the porous walls of the wall-flow filter.
  • the preparation of the catalyst according to the invention can according to the
  • the average particle size of the SCR catalytically active materials is preferably selected such that both the material zone A and the material zone B are located in the porous walls which form the channels of the wall-flow filter, ie a coating of the internal pore surfaces takes place (in -Wand coating). In this case, the middle one must be selected such that both the material zone A and the material zone B are located in the porous walls which form the channels of the wall-flow filter, ie a coating of the internal pore surfaces takes place (in -Wand coating). In this case, the middle one must be selected such that both the material zone A and the material zone B are located in the porous walls which form the channels of the wall-flow filter, ie a coating of the internal pore surfaces takes place (in -Wand coating). In this case, the middle one must be selected such that both the material zone A and the material zone B are located in the porous walls which form the channels of the wall-flow filter, ie a coating of the internal pore surfaces takes place (in -Wand
  • Particle size of the SCR catalytically active materials be small enough to penetrate into the pores of the wall flow filter.
  • the present invention also includes embodiments in which one of the material zones A and B in-wall and the other is coated on-wall.
  • the present invention also relates to embodiments in which the catalyst substrate is formed from an inert matrix component and the SCR catalytically active material A or B and the other SCR catalytically active material, ie. Material B or A, in the form of a material zone B or A at least over a part of the length L of
  • Catalyst substrate extends.
  • Catalyst substrates, flow-through substrates as well as wall-flow filters which not only consist of inert material, such as cordierite, for example, but which also contain a catalytically active material, are known to the person skilled in the art.
  • inert material such as cordierite, for example
  • catalytically active material for their preparation, a mixture of, for example, 10 to 95% by weight of inert matrix component and 5 to 90% by weight of catalytically active material is extruded by processes known per se.
  • matrix components all else can be used for
  • catalyst substrates used inert materials can be used. These are, for example, silicates, oxides, Nitrides or carbides, with particular preference being given to magnesium-aluminum silicates.
  • extruded catalyst substrates comprising SCR catalytically active material A or B, as inert catalyst substrates can also be coated by conventional methods.
  • a catalyst substrate comprising SCR catalytically active material B can be coated over its entire length or a part thereof with a washcoat containing the SCR catalytically active
  • Material A contains.
  • a catalyst substrate comprising SCR catalytically active material A can be coated over its entire length or a part thereof with a washcoat which contains the SCR catalytically active material B.
  • the SCR-active coating catalysts according to the invention can advantageously be used for purifying exhaust gas from lean-burn internal combustion engines, in particular from diesel engines. They are to be arranged in the exhaust gas stream in such a way that material zone A comes into contact with the exhaust gas to be cleaned upstream of material zone B. In the exhaust gas contained nitrogen oxides are thereby converted into the harmless compounds nitrogen and water.
  • the present invention accordingly also relates to a method for
  • the reducing agent used in the process according to the invention is preferably ammonia.
  • the required ammonia can be formed, for example, in the exhaust system upstream of the catalyst according to the invention, for example by means of an upstream nitrogen oxide storage catalytic converter (lean NOx trap - LNT). This method is known as "passive SCR".
  • ammonia can also be carried in the form of an aqueous urea solution on board a vehicle, which is metered in as required via an injector upstream of the catalyst according to the invention.
  • the present invention thus also relates to a system for purifying exhaust gas from lean-burn internal combustion engines, which is characterized in that it comprises an SCR-active coating catalyst according to the invention, and an aqueous urea solution injector, wherein the injector prevails before the first end of the Catalyst substrate is located.
  • the inventive system for purifying exhaust gas of lean-burn internal combustion engines it thus comprises in the flow direction of the exhaust gas, an oxidation catalyst, an injector for aqueous urea solution and a novel
  • platinum on a support material is used as the oxidation catalyst.
  • Suitable carrier material for the platinum are all those skilled in the art for this purpose materials into consideration. They have a BET surface area of from 30 to 250 m 2 / g, preferably from 100 to 200 m 2 / g (determined to DIN 66132) and are in particular aluminum oxide, silicon oxide, Magnesium oxide, titanium oxide, zirconium oxide, cerium oxide and mixtures or mixed oxides of at least two of these oxides.
  • the oxidation catalyst is usually on a
  • Flow-through substrate in particular a flow-through substrate made of cordierite.
  • a conventional cordierite wall-flow filter was made from one end to 50% of its length by means of a conventional
  • the SAR value of the zeolite was 30.
  • the filter was dried at 120 ° C.
  • the wall-flow filter obtained in step a) was coated in a second step from its other end also to 50% of its length by means of a conventional dipping process with a washcoat containing a zeolite exchanged with 3.5 wt .-% Cu from Levyne Structure type contained.
  • the SAR value of the zeolite was 31.
  • Example 1 was repeated with the difference that instead of a conventional wall flow filter made of cordierite a conventional
  • Example 2 was repeated with the difference that in step a) 250 g / l of substrate of the 4.0 wt .-% Cu exchanged chabazite-type zeolite and in step b) already used in step a) with 4.0 Wt .-% Cu exchanged zeolite of chabazite structure type in an amount of 150 g / l substrate was applied.
  • Test procedure area 2c determined. For each temperature point above 500 ° C (space velocity 100k h -1 ), the equilibrium conversion was determined in the test procedure area 2c The N 2 O concentration was determined at all temperature points by FT-IR From the plot of NOx conversion and N 2 O concentration for the different temperature points, a plot results as shown in FIG.
  • Example 2 The catalyst according to Example 2 was once tested so that the model gas came into contact first with the Cu-Levyne and then with the Cu-chabazite. This measurement is designated as an example 2/1 in FIG. In addition, the catalyst according to Example 2 was also tested "reversed" so that the model gas came into contact first with the Cu chabazite and then with the Cu levyne, this measurement being designated in Figure 1 as Example 2/2.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Exhaust Gas After Treatment (AREA)
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Abstract

L'invention concerne un catalyseur comprenant un substrat de longueur L et deux matériaux A et B à effet catalytique SCR, le matériau A à effet catalytique SCR contenant une zéolithe dont la structure est de type levyne et qui contient du fer et/ou du cuivre à ions échangés, et le matériau B à effet catalytique SCR contenant une zéolithe dont la structure est de type chabazite et qui contient du fer et/ou du cuivre à ions échangés, (i) les matériaux A et B à effet catalytique SCR étant présents sous la forme de deux zones de matériaux A et B, la zone de matériau A s'étendant à partir de la première extrémité du substrat de catalyseur au moins sur une partie de la longueur L et le matériau B s'étendant à partir de la deuxième extrémité du substrat de catalyseur au moins sur une partie de la longueur L, ou (ii) le substrat de catalyseur étant formé à partir du matériau A ou B à effet catalytique SCR et à partir d'un composant matrice et le matériau B ou A à effet catalytique SCR s'étendant sous la forme d'une zone de matériau B ou A au moins sur une partie de la longueur L du substrat de catalyseur.
PCT/EP2017/058900 2016-04-13 2017-04-13 Catalyseur pourvu d'un revêtement à effet scr WO2017178575A1 (fr)

Priority Applications (7)

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US16/086,720 US20190105650A1 (en) 2016-04-13 2017-04-13 Catalyst having scr-active coating
KR1020187032743A KR20180127514A (ko) 2016-04-13 2017-04-13 Scr-활성 코팅을 갖는 촉매
JP2018543128A JP7013378B2 (ja) 2016-04-13 2017-04-13 Ｓｃｒ活性コーティングを有する触媒
CN202111514436.9A CN114160188A (zh) 2016-04-13 2017-04-13 具有scr活性涂层的催化剂
EP17716275.7A EP3442686A1 (fr) 2016-04-13 2017-04-13 Catalyseur pourvu d'un revêtement à effet scr
CN201780010184.1A CN108712927B (zh) 2016-04-13 2017-04-13 具有scr活性涂层的催化剂
JP2022005655A JP7322206B2 (ja) 2016-04-13 2022-01-18 Ｓｃｒ活性コーティングを有する触媒

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US20220154611A1 (en) * 2019-04-15 2022-05-19 Basf Corporation A selective catalytic reduction catalyst on a filter
EP3782726A1 (fr) * 2019-08-20 2021-02-24 Umicore Ag & Co. Kg Catalyseur pour la réduction des emissions d'ammoniac et d'oxydes d'azote provenant des gaz d'échappement de moteurs à combustion interne

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EP3442686A1 (fr) 2019-02-20
CN114160188A (zh) 2022-03-11
KR20180127514A (ko) 2018-11-28
JP7013378B2 (ja) 2022-02-15
CN108712927B (zh) 2022-01-04
JP2019518587A (ja) 2019-07-04
JP2022058647A (ja) 2022-04-12
JP7322206B2 (ja) 2023-08-07
US20190105650A1 (en) 2019-04-11

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